U.S. patent number 6,063,848 [Application Number 08/894,268] was granted by the patent office on 2000-05-16 for liquid crystalline polymer composition and moldings.
This patent grant is currently assigned to Polyplastics Co., Ltd.. Invention is credited to Kazuhito Kobayashi, Haruji Murakami.
United States Patent |
6,063,848 |
Murakami , et al. |
May 16, 2000 |
Liquid crystalline polymer composition and moldings
Abstract
The present invention provides a liquid crystal polymer
composition wherein the low coefficient of linear expansion is
attained without significantly deteriorating mechanical properties
by incorporating plural fibrous fillers or a fibrous filler and a
particulate filler with liquid crystal polymer in a specified
ratio.
Inventors: |
Murakami; Haruji (Shizuoka,
JP), Kobayashi; Kazuhito (Shizuoka, JP) |
Assignee: |
Polyplastics Co., Ltd. (Osaka,
JP)
|
Family
ID: |
18336641 |
Appl.
No.: |
08/894,268 |
Filed: |
September 8, 1997 |
PCT
Filed: |
December 27, 1996 |
PCT No.: |
PCT/JP96/03880 |
371
Date: |
September 08, 1997 |
102(e)
Date: |
September 08, 1997 |
PCT
Pub. No.: |
WO97/24404 |
PCT
Pub. Date: |
October 07, 1997 |
Foreign Application Priority Data
|
|
|
|
|
Dec 27, 1995 [JP] |
|
|
7-340405 |
|
Current U.S.
Class: |
524/413;
524/456 |
Current CPC
Class: |
C08K
7/04 (20130101); C08L 77/12 (20130101); C08L
101/00 (20130101); C08L 101/12 (20130101); C08L
2205/12 (20130101); C08K 2201/016 (20130101) |
Current International
Class: |
C08L
101/12 (20060101); C08L 101/00 (20060101); C08K
7/00 (20060101); C08L 77/00 (20060101); C08K
7/04 (20060101); C08L 77/12 (20060101); C08K
003/10 () |
Field of
Search: |
;524/494,413,456 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
|
|
|
|
|
3-243648 |
|
Oct 1991 |
|
JP |
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4-076049 |
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Mar 1992 |
|
JP |
|
6-172619 |
|
Jun 1994 |
|
JP |
|
6-240114 |
|
Aug 1994 |
|
JP |
|
Primary Examiner: Michl; Paul R.
Attorney, Agent or Firm: Burns, Doane, Swecker & Mathis,
L.L.P.
Claims
We claim:
1. A liquid crystal polymer composition which forms upon injection
molding a molding having a coefficient of linear expansion in any
direction at an atmosphere temperature of 50.degree. C. of
4.0.times.10.sup.-5 /.degree. C. or less comprising 100 parts by
weight of a liquid crystal polymer (A), a fibrous filler (B)
selected from the group consisting of wollastonite, potassium
titanate fiber, and mixtures thereof having an average fiber
diameter of 0.1 to 8.0 .mu.m and an average aspect ratio of at
least 3, and a fibrous filler (C) having an average fiber diameter
of 8.5 to 20.0 .mu.m and average aspect ratio of 40 or below, the
total amount of the components (B) and (C) being 100 to 240 parts
by weight, and the ratio of the component (B) to the component (C)
being 1:3 to 3:1.
2. The composition according to claim 1, wherein the ratio of the
component (B) to the component (C) is 1:2 to 2:1.
3. The composition according to claim 1, wherein the liquid crystal
polymer (A) is a polyester amide.
4. A liquid crystal polymer composition which forms upon injection
molding a molding having a coefficient of linear expansion in any
direction at an atmosphere temperature of 50.degree. C. of
4.0.times.10.sup.-5 /.degree. C. or less comprising 100 parts by
weight of a liquid crystal polymer (A), fibrous filler (B) selected
from the group consisting of wollastonite, potassium titanate
fiber, and mixtures thereof having an average fiber diameter of 0.1
to 8.0 .mu.m and an average aspect ratio of at least 3, and a
particulate filler (D) having an average particle diameter of 100
.mu.m or below, the total amount of the components (B) and (D)
being 100 to 240 parts by weight, and the ratio of the component
(B) to the component (D) being 1:3 to 3:1.
5. The composition according to claim 4, wherein the ratio of the
component (B) to the component (D) is 1:2 to 2:1.
6. The composition according to claim 4, wherein the particulate
filler (D) is glass beads.
7. The composition according to claim 4, wherein the liquid crystal
polymer (A) is a polyester amide.
8. A molding produced from the liquid crystal polymer composition
according to claim 1, wherein the coefficient of linear expansion
thereof is 4.0.times.10.sup.-5 /.degree. C. or less in any
direction at the atmospheric temperature of 50.degree. C.
9. A molding produced from the liquid crystal polymer composition
according to claim 5, wherein the coefficient of linear expansion
thereof is 4.0.times.10.sup.-5 /.degree. C. or less in any
direction at the atmospheric temperature of 50.degree. C.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a composition comprising of plural
fibrous fillers, or a fibrous filler and a particulate filler, and
liquid crystal polymer. More particularly, the present invention
relates to molding with extremely low coefficient of linear
expansion produced from the liquid crystal polymer composition.
2. Description of Related Art
Liquid crystal polymers which can form anisotropic melting phase
are materials known to have low coefficient of linear expansion
among thermoplastic resins. Recently, however, for high accuracy,
labor saving, reduction of weight, reduction of cost, the
requirements have been becoming stricter in the field of electrical
and electronic field. With improvement of adhesive technique
between resin parts and metallic ones, such resin parts have been
often used with metallic parts. Under the circumstances, there are
demand for thermoplastic resins having coefficient of linear
expansion similar to that of thermoset resins or metal. Liquid
crystal polymer, which is a material having lower coefficient of
linear expansion for thermoplastic resins, and has higher
coefficient of linear expansion in the direction perpendicular to
flow compared with that in the direction of flow due to its
properties, and is a highly anisotropic material. It is extremely
difficult to reduce anisotropy as well as coefficient of linear
expansion. Therefore, few studies have centered on reduction of
coefficient of linear expansion.
DISCLOSURE OF THE INVENTION
SUMMARY OF THE INVENTION
Considering the above problems, the present inventors have studied
intensively on materials having excellent properties as materials
with less anisotropy and low coefficient of linear expansion. As
the results, we have found that a composition comprising of liquid
crystal polymer and two or more specific fillers can provide
materials with lower coefficient of linear expansion without
significantly deteriorating mechanical properties. Thus, we have
attained the present invention.
That is, the present invention provides a liquid crystal polymer
composition which comprises 100 parts by weight of a liquid crystal
polymer (A), a fibrous filler (B) having an average fiber diameter
of 0.1 to 8.0 .mu.m and an average aspect ratio of at least 3, and
a fibrous filler (C) having an average fiber diameter of 8.5 to
20.0 .mu.m and average aspect ratio of 40 or below, the total
amount of the components (B) and (C) being 100 to 240 parts by
weight, and the ratio of the component (B) to the component (C)
being 1:3 to 3:1.
In addition, the present invention provides a liquid crystal
polymer composition which-comprises 100 parts by weight of a liquid
crystal polymer (A), fibrous filler (B) having an average fiber
diameter of 0.1 to 8.0 .mu.m and an average aspect ratio of at
least 3, and a particulate filler (D) having an average particle
diameter of 100 .mu.m or below, the total amount of the components
(B) and (D) being 100 to 240 parts by weight, and the ratio of the
component (B) to the component (D) being 1:3 to 3:1.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be illustrated in detail.
A liquid crystal polymer (A) used in the present invention means
melt-fabricable polymer which can form optically anisotropic
melting phase.
The characteristics of anisotropic melting phase can be confirmed
by the conventional polarization assay utilizing rectangular
polarizers. More particularly, anisotropic melting phase can be
confirmed using Leitz polarization microscope by observing molten
sample mounted on a Leitz hot stage under an atmosphere of nitrogen
at 40.times. magnifications. Liquid crystal polymer applicable to
the present invention exhibits optical anisotropy upon examination
between rectangular polarizers, wherein polarized light generally
permeates even if in a melting static state.
The aforementioned liquid crystal polymer (A) is not particularly
limited, but preferably aromatic polyester or aromatic polyester
amide. Polyester which partially contains aromatic polyester or
aromatic polyesteramide in the same molecular chain is also
encompassed. Those having inherent viscosity (I.V.) of at least
about 2.0 dl/g, more preferably 2.0 to 10.0 dl/g when dissolved in
pentafluorophenol at 60.degree. C. at the concentration of 0.1% by
weight may be used.
Aromatic polyester or aromatic polyester amide for the liquid
crystal polymer (A) applicable to the present invention includes,
particularly preferably, aromatic polyester and aromatic polyester
amide having, as a constituent, at least one compound selected from
the group consisting of aromatic hydroxycarboxylic acid, aromatic
hydroxyamine, aromatic diamine. More particularly, (1) polyester
mainly consisting of one or two or more aromatic hydroxycarboxylic
acid and derivative thereof; (2) polyester mainly consisting of (a)
one or two or more aromatic hydroxycarboxylic acid and derivative
thereof; (b) one or two or more aromatic dicarboxylic acid,
alicyclic dicarboxylic acid and derivative thereof; (c) at least
one or two or more aromatic diol, alicyclic diol, aliphatic diol
and derivative thereof; (3) polyester amide mainly consisting of
(a) one or two or more aromatic hydroxycarboxylic acid and
derivative thereof; (b) one or two or more aromatic hydroxyamine,
aromatic diamine and derivative thereof; (c) one or two or more
aromatic dicarboxylic acid, alicyclic dicarboxylic acid and
derivative thereof; (4) polyester amide mainly consisting of (a)
one or two or more aromatic hydroxycarboxylic acid and derivative
thereof; (b) one or two or more aromatic hydroxyamine, aromatic
diamine and derivative thereof; (c) one or two or more aromatic
dicarboxylic acid, alicyclic dicarboxylic acid and derivative
thereof; (d) at least one or two or more aromatic diol, alicyclic
diol, aliphatic diol and derivative thereof. Moreover, the
aforementioned constituents may be used along with a molecular
weight modifier, as needed.
Preferred example of the concrete compounds constituting the
aforementioned liquid crystal polymer (A) applicable to the present
invention includes, for example, aromatic hydroxycarboxylic acid
such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid;
aromatic diol such as 2,6-dihydroxynaphthalene,
1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone,
resorcin and compounds represented by the following formulae [1]
and [2]; aromatic dicarboxylic acid such as terephthalic acid,
isophthalic acid, 4,4'-diphenyldicarboxylic acid,
2,6-naphthalenedicarboxylic acid and compounds represented by the
following formula [3]; aromatic amine such as p-aminophenol and
p-phenylenediamine. ##STR1## [wherein, X is a group selected from
alkylene(C.sub.1 -C.sub.4), alkylydene, --O--, --SO--, --SO.sub.2
--, --S--, --CO--; Y is a group
selected from --(CH.sub.2).sub.n -- (in which, n is 1 to 4),
--O(CH.sub.2).sub.n O--, (in which, n is 1 to 4)].
Particularly preferred liquid crystal polymer (A) applicable to the
present invention is aromatic polyester amide containing
6-hydroxy-2-naphthoic acid, terephthalic acid, and p-aminophenol as
constituents.
To attain an object of the present invention, low coefficient of
linear expansion, fibrous filler (B) having average fiber diameter
of 0.1 to 8.0 .mu.m and average aspect ratio of at least 3; and
fibrous filler (C) having average fiber diameter of 8.5 to 20.0
.mu.m and average aspect ratio of 40 or below, preferably 20 or
below are used, and the total amount should be 100 to 240 parts by
weight. That is, two fibrous fillers with different fiber diameter
should be used. Among the fibrous fillers with greater average
fiber diameter which have great reinforcing effect, fibrous fillers
with lower average fiber diameter exist to fill up, thereby
attaining low coefficient of linear expansion without anisotropy
and enhancing reinforcing effect. Accordingly, product with such
low coefficient of linear expansion can not be obtained using
fibrous fillers with the same average fiber diameter.
In this case, if average fiber diameter of the component (C) is
greater than 20.0 .mu.m, the defects of the fibrous filler itself
may increase and the mechanical properties of the fibrous filler
itself may decrease, undesirably resulting in poor reinforcing
effect to be expected. On the other hand, if the average aspect
ratio is more than 40, coefficient of linear expansion in the
direction of flow will be further reduced due to orientation of
fibers, while it will increase in the direction of perpendicular to
that of flow, which is undesirable.
In the present invention, as fibrous filler (B) having average
fiber diameter of 0.1 to 8.0 .mu.m and average aspect ratio of at
least 3, various organic fibers such as carbon fibers, whiskers,
metallic fibers, inorganic fibers and mineral fibers can be
used.
Examples of these fillers will be illustrated below.
As carbon fibers, PAN fibers prepared from polyacrylonitrile, pitch
fibers prepared from pitch can be used.
As whiskers, silicon nitride whiskers, silicon trinitride whiskers,
basic magnesium sulfate whiskers, barium titanate whiskers, silicon
carbide whiskers, boron whiskers, etc.; and as metallic fibers,
fibers of soft steel, stainless steel, steel and alloy thereof,
brass, aluminum and alloy thereof, lead, etc. may be used.
As inorganic fibers, various fibers such as rock wool, zirconia,
alumina-silica, potassium titanate, barium titanate, silicon
carbide, alumina, silica and blast furnace slag, etc. may be
used.
As mineral fibers, asbestos, wollastonite and the like may be
used.
Among them, wollastonite is preferred considering cost and
efficiency.
In the present invention, as fibrous filler (C) having average
fiber diameter of 8.5 to 20.0 .mu.m and average aspect ratio of 40
or below, milled fiber, etc. may be used.
Example of these fillers will be illustrated below.
As milled fibers, in addition to the conventional milled glass
fibers, milled fibers coated with metal such as nickel and copper,
silane fibers and the like may be used.
As alternative method to attain low coefficient of linear
expansion, fibrous filler (B) having average fiber diameter of 0.1
to 8.0 .mu.m and average aspect ratio of at least 3 and particulate
filler (D) having average particle diameter of 100 .mu.m or below
may be used, wherein the total amount should be 100 to 240 parts by
weight.
In this case, it is important to use aforementioned fillers as
fibrous fillers (B). When fillers having average fiber diameter
more than 8.0 .mu.m, it is difficult to attain homogeneous
dispersion with particulate fillers even if the fillers have
average aspect ratio at least 3, undesirably resulting in
deteriorated mechanical properties. When the average aspect ratio
is 3 or below, reinforcing effect of the fibrous fillers may not be
expected, which is undesirable.
In the present invention, particulate fillers means particle-shaped
material which does not extend in specific directions like fiber,
disc, strip, etc., and has average aspect ratio of 1 to 2. The
average particle diameter is 100 .mu.m or below, preferably 1 to 50
.mu.m. It is important to use particulate fillers having average
particle diameter of 100 .mu.m or below. Using those having average
diameter more than 100 .mu.m, the probability of mutual contact of
particulate fillers becomes higher, undesirably resulting in
difficulty of homogenous dispersion and deterioration of mechanical
properties. For example, those consisting of kaolin, clay,
vermiculite, calcium silicate, aluminum silicate, feldspar powder,
acid clay, agalmatolite clay, sericite, sillimanite, bentonite,
gohun, carbonate such as barium carbonate, magnesium carbonate and
dolomite, sulfate such as barytes, branfix, precipitated calcium
sulfate, calcined gypsum and barium sulfate, hydroxide such as
hydrated alumina, alumina, oxide such as antimony oxide, magnesia,
titanium oxide, zinc white, quartz sand, quartz, white carbon and
diatomaceous earth, sulfide such as molybdenum disulfide, metal
powder, organic polymer such as fluororesin, organic low molecular
crystal such as diphenyl ether bromide. Among them, glass beads are
preferred considering cost and efficiency.
As mentioned above, it is important to use two types of fillers
having specific shapes. To attain low coefficient of linear
expansion, the amount and ratio of components of fillers are also
important requirement. That is, to attain low coefficient of linear
expansion, greater amount of filler is preferred. However, too much
filler will deteriorate extrudability and moldability, and further
deteriorate mechanical strength. On the other hand, too little
amount will fail to attain low coefficient of linear expansion.
Accordingly, the total amount of the filler components should be
100 to 240 parts by weight, preferably 140 to 185 parts by weight
based on 100 parts by weight of liquid crystal polymer (A).
In this case, fibrous fillers (B) are useful for improve low
coefficient of linear expansion and mechanical properties. However,
too much amount will deteriorate extrusion ability, resulting in
fragile material. Fibrous fillers (C) are useful for improve low
coefficient of linear expansion and mechanical properties. However,
too much amount will increase anisotropy of the material.
Particulate filler will promote low coefficient of linear expansion
and reduce anisotropy of the material, however, too much fillers
will lead to deterioration of mechanical properties. Accordingly,
to attain the object of the present invention, the ratio of the
fibrous fillers (B) to fibrous fillers (C) or particulate fillers
(D) is 1:3 to 3.1, preferably 1:2 to 2:1, more preferably 2:3 to
3:2.
Fibrous and particulate fillers used in the present invention may
be directly used, but they may be used along with the generally
used, known surface treatment agent, greige goods.
Additives such as nucleating agents, pigment such as carbon black,
antioxidants, stabilizers, plasticizers, lubricant, mold releasing
agents and flame retardants may be added to the thermoplastic
composition to provide thermoplastic composition imparted with the
desired properties, which are encompassed within the category of
the thermoplastic resin compositions according to the present
invention.
The injection-molded articles of the present invention are prepared
by using two or more fillers to offset the mutual defects, thereby
reducing anisotropy characteristic of liquid crystal polymer and
providing low coefficient of linear expansion without deteriorating
mechanical properties. Further, individual filler is homogeneously
dispersed in the molding, and higher efficiency is exhibited by the
dispersion state wherein the second fillers exist among the first
ones.
As mentioned above, the present invention relates to
injection-molded articles suitable which are moldings having in any
directions low coefficient of linear expansion of
4.0.times.10.sup.-5 /.degree. C. or below, suitable to be used
along with metallic parts, and suitable in the recent field of
electric and electronic parts.
To produce aforementioned thermoplastic resin composition, the both
fillers may be compounded at the compounding ratio and kneaded. In
general, the material is kneaded in an extruder, extruded into
pellets and used for injection molding. It is not particularly
limited to kneading using an extruder.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows an ASTM tensile test piece used for measurement of
coefficient of linear expansion in Examples and a cutaway view
thereof.
FD: direction of flow (18.sup.L .times.12.5.sup.W
.times.3.sup.T)
TD: transverse direction (19.sup.L .times.12.5.sup.W
.times.3.sup.T)
EXAMPLE
The present invention will be illustrated in detail in the
following Examples. The present invention is not construed to be
limited to them. The methods for evaluation are as follows:
(Coefficient of linear expansion)
ASTM Tensile test pieces were cut as shown in FIG. 1 were used and
coefficient of linear expansion (.times.10.sup.-5 /.degree. C.) was
measured using a thermal dilatometer by differential measurement of
expansion manufactured by Rigaku Denki KK. Coefficient of linear
expansion was expressed as data at 50.degree. C.
(Flexural modulus of elasticity)
According to ASTM D790, flexural modulus of elasticity (MPa) was
measured using a test piece of 3.2 mm thickness for flexural
test.
(Fiber length of fillers)
Tensile test pieces were cut into appropriate size, charged in a
crucible placed in an electric furnace at 600.degree. C. to
eliminate resin components. Subsequently, residual fillers were
dispersed in 5% aqueous solution of polyethylene glycol, and spread
on Petri dish preventing fillers from overlapping each other. The
fillers were projected using a magnifying projector and 100 of the
fillers were measured to obtain average fiber length.
(Fiber diameter or particle diameter of fillers)
The residual filler obtained in the same manner as described for
measurement of fiber length was dispersed on a sample bed for
scanning electron microscope and observed at the magnification fit
for fiber diameter or particle diameter. Among them, 100 of fillers
were measured to obtain average fiber diameter or particle
diameter.
According to the above results, average aspect ratio of filler was
obtained.
Examples 1, 2 and Comparative Examples to 3
Based on 100 parts by weight of liquid crystal polyester
(manufactured by Polyplastics KK, Vectra A950), wollastonite
(average fiber diameter, 3.5 .mu.m; average aspect ratio, 20) and
milled glass fiber (average fiber diameter, 13 .mu.m; average
aspect ratio, 5.4) were dry blended in the ratio shown in Table 1,
after which molten and kneaded using a biaxial extruder to
pelletize. The obtained pellets were molded using an injection
molding machine to prepare pieces for tensile test (thickness, 3
mm) and for flexural test (thickness, 3.2 mm). The obtained test
pieces were measured for coefficient of linear expansion and
flexural elasticity to obtain the results shown in Table 1.
Comparative Example 4
The procedure in Example 1 was repeated, except that glass fibers
(chopped strand of average fiber diameter, 10 .mu.m; and fiber
length, 3 mm) were used instead of wollastonite, to prepare test
pieces and evaluated. The results are shown in Table 1.
Comparative Examples 5 and 6
In the same manner as in Example 1, test pieces were prepared for
the case using only 100 parts by weight of wollastonite and for the
case using only 100 parts by weight of milled glass fiber, and
evaluated. The results are shown in Table 1.
Examples 3 and 4 and Comparative Examples 7 to 9
Based on 100 parts by weight of liquid crystal polyester
(manufactured by Polyplastics KK, Vectra A950), wollastonite
(average fiber diameter, 3.5 .mu.m; average aspect ratio, 20) and
glass beads (average particle diameter, 50 .mu.m) were dry blended
in the ratio shown in Table 2, after which melt kneaded using a
biaxial extruder to pelletize. The obtained pellets were molded
using an injection molding machine to prepare pieces for tensile
test (thickness, 3 mm) and for flexural test (thickness, 3.2 mm).
The obtained test specimen was measured for coefficient of linear
expansion and flexural elasticity to obtain the results shown in
Table 2.
Comparative Example 10
The procedure in Example 3 was repeated, except that glass fiber
(chopped strand of average fiber diameter, 10 .mu.m; and fiber
length, 3 mm) was used instead of wollastonite, to prepare test
pieces which were measured. The results are shown in Table 2.
Comparative Example 11
In the same manner as in Example 3, except that glass beads having
average particle diameter of 120 .mu.m were used, test pieces were
prepared and evaluated. The results are shown in Table 2.
Example 5
Based on 100 parts by weight of liquid crystal polyester
(manufactured by Polyplastics KK, Vectra A950), potassium titanate
fiber (average fiber diameter, 0.3 .mu.m; average aspect ratio, 50)
and glass beads (average particle diameter, 50 .mu.m) were dry
blended in the ratio shown in Table 2, after which melt kneaded
using a biaxial extruder and pelletized. Such pellets were molded
using an injection molding machine to prepare pieces for stretching
test (thickness, 3 mm) and for flexural test (thickness, 3.2 mm).
The obtained test pieces were measured for coefficient of linear
expansion and flexural elasticity to obtain the results shown in
Table 2.
Comparative Example 12
In the same manner as in Example 5, except that a ratio of
potassium titanate fibers to glass beads was changed as shown in
Table 2, test specimens were prepared and evaluated. The results
are shown in Table 2.
Comparative Example 13
For the case using 100 parts by weight of glass beads alone, test
pieces were prepared and evaluated in the same manner as in Example
5. The results are shown in Table 2.
Example 6 and Comparative Examples 14 and 15
Based on 100 parts by weight of polyester amide (manufactured by
Polyplastics KK, Vectra B950), wollastonite (average fiber
diameter, 3.5 .mu.m; average aspect ratio, 20) and glass beads
(average particle diameter, 50 .mu.m) were dry blended in the ratio
shown in Table 3, after which melt kneaded using a biaxial extruder
and pelletized. Such pellets were molded using an injection molding
machine to prepare pieces for tensile test (thickness, 3 mm) and
for flexural test (thickness, 3.2 mm). The obtained test specimen
was measured for coefficient of linear expansion and flexural
elasticity to obtain the results shown in Table 3.
Example 7
In the same manner as in Example 6, except that glass beads were
substituted with milled glass fibers (average fiber diameter, 13
.mu.m; average aspect ratio, 5.4), test pieces were prepared and
evaluated. The results are shown in Table 3.
Comparative Example 16
Based on 100 parts by weight of liquid crystal polyester amide
(manufactured by Polyplastics KK, Vectra B950), 75 parts by weight
of wollastonite (average fiber diameter, 3.5 .mu.m; average aspect
ratio, 20) were dry blended, melt kneaded using a biaxial extruder,
glass fibers (chopped strand of average fiber diameter, 10 .mu.m;
fiber length, 3 mm) were side fed and pelletized. Such pellets were
molded using an injection molding machine to prepare pieces for
tensile test (thickness, 3 mm) and for flexural test (thickness,
3.2 mm). The obtained test pieces were measured for coefficient of
linear expansion and flexural elasticity to obtain the results
shown in Table 3.
TABLE 1
__________________________________________________________________________
Filler Ex. 1 Ex. 2 Com. Ex. 1 Com. Ex. 2 Com. Ex. 3 Com. Ex. 4 Com.
Ex. 5 Com. Ex. 6
__________________________________________________________________________
(B) First Type Wollastonite Wollastonite Wollastonite Wollastonite
Wollastonite GF -- -- Filler Amount added 75 100 45 100 20 75 --
100 (Parts by Average fiber 3.5 3.5 3.5 3.5 3.5 10 -- 3.5 weight)
diameter (.mu.m) Average aspect 20 20 20 20 20 23 -- 20 ratio (C)
Type MF MF MF MF MF MF MF -- Second Amount added 75 100 45 20 100
75 100 -- Filler Average fiber 13 13 13 13 13 13 13 -- (Parts by
diameter (.mu.m) weight) Average aspect 5.4 5.4 5.4 5.4 5.4 5.4 5.4
-- ratio Coefficient of FD 0.52 0.49 0.80 0.60 0.87 0.42 1.01 0.63
Linear Expansion TD 3.12 3.11 4.60 5.02 4.82 4.08 4.82 5.42
(.times.10.sup.-5 /.degree. C.) Flexural Elasticity (MPa) 14900
15200 13500 14900 15300 18000 14100 13900
__________________________________________________________________________
* GF: Glass fiber MF: Milled glass fiber
TABLE 2
__________________________________________________________________________
Filler Ex. 3 Ex. 4 Com. Ex. 7 Com. Ex. 8 Com. Ex. 9
__________________________________________________________________________
(B) First Type Wollastonite Wollastonite Wollastonite Wollastonite
Wollastonite Filler Amount added 75 100 45 130 30 (Parts by Average
fiber 3.5 3.5 3.5 3.5 3.5 Weight) diameter (.mu.m) Average aspect
20 20 20 20 20 ratio (C) Type GB GB GB GB GB Second Amount added 75
100 45 130 120 Filler Average 50 50 50 50 50 (Parts by particle
Weight) diameter (.mu.m) Average aspect -- -- -- -- -- ratio
Coefficient of FD 1.53 1.02 1.90 cannot be 1.80 Linear expansion TD
3.10 3.08 4.50 extruded 4.25 (.times.10.sup.-5 /.degree. C.)
Flexural Elasticity (MPa) 12800 13200 9500 11000
__________________________________________________________________________
Filler Com. Ex. 10 Com. Ex. 11 Ex. 5 Com. Ex. 12 Com. Ex. 13
__________________________________________________________________________
(B) First Type GF Wollastonite Potassium Potassium -- Filler
titanate titanate (Parts by fiber fiber Weight) Amount added 75 75
30 130 -- Average fiber 10 3.5 0.3 0.3 -- diameter (.mu.m) Average
aspect 23 20 50 50 -- ratio (C) Type GB GB GB GB GB Second Amount
added 75 75 90 40 100 Filler Average 50 120 50 50 50 (Parts by
particle Weight) diameter (.mu.m) Average aspect -- -- -- -- --
ratio Coefficient of FD 1.20 2.35 0.80 cannot be 2.10 Linear
Expansion TD 4.05 4.56 3.85 extruded 5.20 (.times.10.sup.-5
/.degree. C.) Flexural Elasticity (MPa) 16400 11000 15000 8800
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* GF: Glass fiber GB: Glass beads
TABLE 3
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Filler Ex. 6 Ex. 7 Com. Ex. 14 Com. Ex. 15 Com. Ex. 16
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(B) First Filler Type Wollastonite Wollastonite Wollastonite
Wollastonite Wollastonite (Parts by weight) Amount to be 75 75 45
130 75 added Average fiber 3.5 3.5 3.5 3.5 3.5 diameter (.mu.m)
Average aspect 20 20 20 20 20 ratio (C) Second Filler Type GB MF GB
GB GF (Parts by weight) Amount to be 75 75 45 130 75 added Average
fiber -- 13 -- -- 10 diameter (.mu.m) Average particle 50 -- 50 50
-- diameter (.mu.m) Average aspect -- 5.4 -- -- 45 ratio
Coefficient of Linear FD 0.90 0.78 1.30 cannot be 0.52 Expansion
(.times.10.sup.-5 /.degree. C.) TD 2.26 2.55 4.40 extruded 4.02
Bending Elasticity (MPa) 16200 18600 14000 20100
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* GF: Glass fiber GB: Glass beads MF: Milled glass fiber
* * * * *